WO2018168396A1 - ニトリル基含有共重合体ゴム - Google Patents

ニトリル基含有共重合体ゴム Download PDF

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Publication number
WO2018168396A1
WO2018168396A1 PCT/JP2018/006684 JP2018006684W WO2018168396A1 WO 2018168396 A1 WO2018168396 A1 WO 2018168396A1 JP 2018006684 W JP2018006684 W JP 2018006684W WO 2018168396 A1 WO2018168396 A1 WO 2018168396A1
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containing copolymer
copolymer rubber
group
nitrile group
rubber
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PCT/JP2018/006684
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English (en)
French (fr)
Japanese (ja)
Inventor
敦弘 塩野
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日本ゼオン株式会社
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Priority to EP18766827.2A priority Critical patent/EP3597677B1/en
Priority to CA3056037A priority patent/CA3056037A1/en
Priority to JP2019505822A priority patent/JP7088164B2/ja
Priority to CN201880018369.1A priority patent/CN110461892B/zh
Priority to RU2019128492A priority patent/RU2752164C2/ru
Priority to US16/493,270 priority patent/US20200131293A1/en
Priority to KR1020197027179A priority patent/KR102475647B1/ko
Priority to BR112019019066A priority patent/BR112019019066A2/pt
Priority to MX2019010745A priority patent/MX2019010745A/es
Publication of WO2018168396A1 publication Critical patent/WO2018168396A1/ja
Priority to US17/592,755 priority patent/US11639408B2/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00—Chemical modification of rubber
    • C08C19/02—Hydrogenation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C08F236/14—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated containing elements other than carbon and hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/42—Nitriles
    • C08F220/44—Acrylonitrile
    • C08F220/46—Acrylonitrile with carboxylic acids, sulfonic acids or salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C1/00—Treatment of rubber latex
    • C08C1/14—Coagulation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
    • C08C19/00—Chemical modification of rubber
    • C08C19/22—Incorporating nitrogen atoms into the molecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/42—Nitriles
    • C08F220/44—Acrylonitrile
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C08F236/06—Butadiene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/205—Compounds containing groups, e.g. carbamates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
    • C08K5/3462—Six-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
    • C08K5/3462—Six-membered rings
    • C08K5/3465—Six-membered rings condensed with carbocyclic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L13/00—Compositions of rubbers containing carboxyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/02—Copolymers with acrylonitrile

Definitions

  • the present invention relates to a nitrile group-containing copolymer rubber, and more specifically, a nitrile capable of providing a rubber cross-linked product excellent in processability and excellent in compression set resistance when formed into a rubber cross-linked product.
  • the present invention relates to a group-containing copolymer rubber.
  • Nitrile rubber (acrylonitrile-butadiene copolymer rubber) has been used as a material for automotive rubber parts such as hoses and seals, taking advantage of oil resistance, mechanical properties, chemical resistance, etc.
  • Hydrogenated nitrile rubber (hydrogenated acrylonitrile-butadiene copolymer rubber) in which carbon-carbon double bonds in the polymer main chain of rubber are hydrogenated is further excellent in mechanical properties and heat resistance, so belts, hoses, seals, diaphragms, etc. Used for rubber parts.
  • a hydrogenated nitrile rubber having an ⁇ , ⁇ -ethylenically unsaturated dicarboxylic acid monoester monomer unit, a polyamine-based crosslinking agent, and a basic crosslinking accelerator are disclosed.
  • a nitrile rubber composition containing benzene has been proposed.
  • the viscosity increase is high when a polyamine-based cross-linking agent is blended, and the processability is sufficient. Therefore, further improvement in workability has been desired.
  • the present invention has been made in view of such a situation, and has a nitrile group that can give a rubber cross-linked product with excellent workability and excellent pressure-resistant permanent distortion when made into a rubber cross-linked product.
  • An object is to provide a copolymer rubber.
  • the present inventors have determined that a specific amount of ⁇ , ⁇ -ethylenically unsaturated nitrile monomer unit and a single amount of ⁇ , ⁇ -ethylenically unsaturated dicarboxylic acid monoester
  • the processability is the product of the carboxyl group content and the absorbance area of the carboxylic anhydride group determined by infrared spectroscopy
  • the inventors have found that the above object can be achieved by setting the index within a predetermined range, and have completed the present invention.
  • the nitrile group-containing copolymer rubber of the present invention preferably contains a conjugated diene monomer unit at a content of 20 to 89% by weight.
  • the content of the ⁇ , ⁇ -ethylenically unsaturated dicarboxylic acid monoester monomer unit is preferably 1 to 10% by weight.
  • the ⁇ , ⁇ -ethylenically unsaturated dicarboxylic acid monoester monomer unit is composed of a mono n-butyl maleate unit, a mono n-butyl fumarate unit and a monocyclo fumarate unit.
  • the crosslinkable rubber composition containing said nitrile group containing copolymer rubber and a crosslinking agent is provided.
  • the crosslinkable rubber composition of the present invention preferably further contains a basic crosslinking accelerator having a cyclic amidine structure.
  • crosslinking said crosslinkable rubber composition is provided.
  • a nitrile group-containing copolymer rubber that is excellent in processability and can give a rubber cross-linked product excellent in pressure-resistant permanent distortion when used as a rubber cross-linked product, and such a nitrile It is possible to provide a rubber cross-linked product obtained by using a group-containing copolymer rubber and excellent in pressure-resistant permanent distortion.
  • FIG. 1 is a diagram showing a spectrum of infrared spectroscopic analysis of a nitrile group-containing copolymer rubber according to Production Example 11.
  • the nitrile group-containing copolymer rubber of the present invention comprises an ⁇ , ⁇ -ethylenically unsaturated nitrile monomer unit of 10 to 60% by weight and an ⁇ , ⁇ -ethylenically unsaturated dicarboxylic acid monoester.
  • a nitrile group-containing copolymer rubber containing 1 to 60% by weight of ester monomer units and having an iodine value of 120 or less, Processability index is the product of a carboxyl group content C C is the number of moles of the carboxyl group of the nitrile group-containing copolymer rubber per 100 g, and the absorbance area S A of the carboxylic anhydride group obtained by infrared spectroscopy I pro (I pro C C ⁇ S A ) is controlled to 0.0030 or less.
  • the ⁇ , ⁇ -ethylenically unsaturated nitrile monomer forming the ⁇ , ⁇ -ethylenically unsaturated nitrile monomer unit is not limited as long as it is an ⁇ , ⁇ -ethylenically unsaturated compound having a nitrile group.
  • the ⁇ , ⁇ -ethylenically unsaturated nitrile monomer may be used alone or in combination of two or more.
  • the content ratio of the ⁇ , ⁇ -ethylenically unsaturated nitrile monomer unit in the nitrile group-containing copolymer rubber of the present invention is 10 to 60% by weight, preferably 10 to 50% by weight, more preferably 15 to 45% by weight. If the content ratio of the ⁇ , ⁇ -ethylenically unsaturated nitrile monomer unit is too small, the oil resistance of the resulting rubber cross-linked product is lowered. On the other hand, if the amount is too large, the cold resistance of the resulting rubber cross-linked product is lowered.
  • the ⁇ , ⁇ -ethylenically unsaturated dicarboxylic acid monoester monomer unit forming the ⁇ , ⁇ -ethylenically unsaturated dicarboxylic acid monoester monomer unit includes monomethyl maleate, monoethyl maleate, monopropyl maleate, Maleic acid monoalkyl esters such as mono-n-butyl maleate; maleic acid monocycloalkyl esters such as monocyclopentyl maleate, monocyclohexyl maleate, monocycloheptyl maleate; monomethylcyclopentyl maleate, monoethylcyclohexyl maleate, etc.
  • Monoalkyl cycloalkyl esters of maleic acid monoalkyl esters of fumaric acid such as monomethyl fumarate, monoethyl fumarate, monopropyl fumarate, mono-n-butyl fumarate; monocyclopentyl fumarate, fumaric acid
  • monocycloalkyl esters of fumaric acid such as monocyclohexyl luric acid and monocycloheptyl fumarate
  • monomethylcyclopentyl fumarate monoalkylcycloalkyl fumaric acid such as monoethylcyclohexyl fumarate
  • Citraconic acid monoalkyl esters such as propyl and monon-butyl citraconic acid
  • Citraconic acid monocycloalkyl esters such as citraconic acid monocyclopentyl, citraconic acid monocyclohexyl and citraconic acid monocycl
  • the ⁇ , ⁇ -ethylenically unsaturated dicarboxylic acid monoester monomer may be used alone or in combination of two or more.
  • ⁇ , ⁇ -ethylenically unsaturated dicarboxylic acid monoalkyl ester monomers and ⁇ , ⁇ -ethylenically unsaturated dicarboxylic acid monocycloalkyl ester monomers are more preferred, maleic acid monoalkyl esters, fumaric acid Monoalkyl esters, monocycloalkyl esters of fumaric acid and monoalkyl esters of itaconic acid are more preferred, and mono n-butyl maleate, mono n-butyl fumarate and monocyclohexyl fumarate are particularly preferred.
  • the number of carbon atoms in the alkyl group of the alkyl ester is preferably 2-8.
  • the content ratio of the ⁇ , ⁇ -ethylenically unsaturated dicarboxylic acid monoester monomer unit in the nitrile group-containing copolymer rubber of the present invention is 1 to 60 wt. It is 1 to 20% by weight, more preferably 1 to 10% by weight, still more preferably 3 to 8% by weight.
  • the content ratio of the ⁇ , ⁇ -ethylenically unsaturated dicarboxylic acid monoester monomer unit is too small, the compression set resistance of the resulting rubber cross-linked product is lowered.
  • the amount is too large, the elongation, which is one of the mechanical properties of the resulting rubber cross-linked product, is lowered.
  • the nitrile group-containing copolymer rubber of the present invention preferably also contains a conjugated diene monomer unit so that the resulting cross-linked product has rubber elasticity.
  • conjugated diene monomer forming the conjugated diene monomer unit examples include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, chloroprene and the like having 4 to 4 carbon atoms. 6 conjugated diene monomers are preferred, 1,3-butadiene and isoprene are more preferred, and 1,3-butadiene is particularly preferred.
  • the conjugated diene monomer may be used alone or in combination of two or more.
  • the content of the conjugated diene monomer unit (including the hydrogenated part) is preferably 20 to 89% by weight, more preferably 30 to 80% by weight, and still more preferably based on the total monomer units. 40 to 65% by weight.
  • the rubber crosslinked material obtained can be made excellent in rubber elasticity, maintaining heat resistance and chemical stability favorable.
  • the polymerization conversion rate can be improved by setting the content of the conjugated diene monomer unit to the above lower limit value or more.
  • the nitrile group-containing copolymer rubber of the present invention has an ⁇ , ⁇ -ethylenically unsaturated nitrile monomer unit of 30% by weight or less from the viewpoint that the resulting rubber cross-linked product is excellent in low temperature characteristics.
  • the ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acid ester monomer unit forming the ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acid ester monomer unit includes methyl acrylate, ethyl acrylate, and n-butyl acrylate.
  • (Meth) acrylic acid ester having 1 to 18 carbon atoms such as isobutyl acrylate, n-dodecyl acrylate, methyl methacrylate, ethyl methacrylate, etc. (abbreviation of “methacrylic acid ester and acrylic acid ester”.
  • C 2-18 such as methoxymethyl acrylate, methoxyethyl acrylate, ethoxypropyl acrylate, methoxybutyl acrylate, ethoxydodecyl acrylate, methoxyethyl methacrylate, methoxybutyl methacrylate, ethoxypentyl methacrylate, etc.
  • alkoxyalkyl acrylic acid ester having a cyanoalkyl group having 2 to 12 carbon atoms such as ⁇ -cyanoethyl acrylate, ⁇ -cyanoethyl methacrylate, cyanobutyl methacrylate, etc .
  • 2-hydroxyethyl acrylate acrylic acid esters having a hydroxyalkyl group having 1 to 12 carbon atoms such as 2-hydroxypropyl acrylate and 2-hydroxyethyl methacrylate
  • 1 carbon atoms such as trifluoroethyl acrylate and tetrafluoropropyl methacrylate
  • acrylic acid ester having 12 to 12 fluoroalkyl groups acrylic acid ester having 12 to 12 fluoroalkyl groups
  • a (meth) acrylic acid ester having an alkyl group having 1 to 18 carbon atoms and an alkoxyalkyl group having 2 to 18 carbon atoms from the viewpoint that the cold resistance of the resulting rubber crosslinked product can be further improved.
  • (Meth) acrylic acid esters having the following are preferred: n-butyl acrylate and methoxyethyl acrylate are particularly preferred.
  • the ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acid ester monomer may be used alone or in combination of two or more.
  • the content ratio of the ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acid ester monomer unit in the nitrile group-containing copolymer rubber of the present invention is preferably 0 to 60% by weight, more preferably, in all monomer units. Preferably it is 0 to 50% by weight, more preferably 0 to 40% by weight.
  • the content of ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acid ester monomer units is too high, resulting in a decrease in polymerization conversion rate and strength that is one of the mechanical properties of the resulting rubber cross-linked product. The decrease can be suppressed.
  • the nitrile group-containing copolymer rubber of the present invention includes an ⁇ , ⁇ -ethylenically unsaturated nitrile monomer unit, an ⁇ , ⁇ -ethylenically unsaturated dicarboxylic acid monoester monomer unit, and, if necessary, In addition to the conjugated diene monomer unit and the ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acid ester monomer unit that can be contained, other monomers that can be copolymerized with the monomer that forms them It may contain a body unit.
  • Examples of such other monomers include ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acid monomers, ⁇ , ⁇ -ethylenically unsaturated polycarboxylic acid monomers ( ⁇ , ⁇ -ethylenically unsaturated monomers). Excluding those corresponding to dicarboxylic acid monoester monomers), ethylene, ⁇ -olefin monomers, aromatic vinyl monomers, fluorine-containing vinyl monomers, copolymerizable antioxidants, etc. .
  • Examples of the ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acid monomer include acrylic acid, methacrylic acid, ethyl acrylic acid, crotonic acid, and cinnamic acid.
  • Examples of the ⁇ , ⁇ -ethylenically unsaturated polyvalent carboxylic acid monomer include butenedionic acid such as fumaric acid and maleic acid, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, allylmalonic acid, and teraconic acid.
  • Examples of the anhydride of ⁇ , ⁇ -unsaturated polyvalent carboxylic acid include maleic anhydride, itaconic anhydride, citraconic anhydride, and the like.
  • the ⁇ -olefin monomer preferably has 3 to 12 carbon atoms, and examples thereof include propylene, 1-butene, 4-methyl-1-pentene, 1-hexene and 1-octene.
  • aromatic vinyl monomer examples include styrene, ⁇ -methylstyrene, vinyl pyridine and the like.
  • fluorine-containing vinyl monomer examples include fluoroethyl vinyl ether, fluoropropyl vinyl ether, o-trifluoromethylstyrene, vinyl pentafluorobenzoate, difluoroethylene, and tetrafluoroethylene.
  • copolymerizable anti-aging agents examples include N- (4-anilinophenyl) acrylamide, N- (4-anilinophenyl) methacrylamide, N- (4-anilinophenyl) cinnamamide, N- (4-anilino). Phenyl) crotonamide, N-phenyl-4- (3-vinylbenzyloxy) aniline, N-phenyl-4- (4-vinylbenzyloxy) aniline and the like.
  • the content of other monomer units is preferably 50% by weight or less, more preferably 40% by weight or less, and still more preferably 10%, based on all monomer units constituting the nitrile group-containing copolymer rubber. % By weight or less.
  • the iodine value of the nitrile group-containing copolymer rubber of the present invention is 120 or less, preferably 60 or less, more preferably 50 or less, and particularly preferably 30 or less. If the iodine value of the nitrile group-containing copolymer rubber is too high, the heat resistance and ozone resistance of the resulting rubber cross-linked product may be lowered.
  • a carboxyl group content C C is the number of moles of the carboxyl group of the nitrile group-containing copolymer rubber per 100 g, the carboxylic acid anhydride obtained by infrared spectroscopic analysis
  • the workability index I pro by setting the workability index I pro to 0.0030 or less, an increase in Mooney viscosity when a crosslinking agent is blended can be suppressed to a low level.
  • the moldability in the case of blending various compounding agents including can be improved.
  • the carboxyl group content CC is the number of moles of carboxyl groups per 100 g of the nitrile group-containing copolymer rubber, and can be measured, for example, by the following method. That is, the nitrile group-containing copolymer rubber was dissolved in a predetermined solvent, and the resulting nitrile group-containing copolymer rubber solution was titrated using an alkali to determine the number of moles of carboxyl groups relative to 100 g of rubber (esterification). The number of moles of free carboxyl groups that are not equal can be calculated.
  • the carboxyl group content C C is preferably 0.005 to 0.116 ephr, more preferably 0.005 to 0.058 ephr, and particularly preferably 0.015 to 0.046 ephr. As the carboxyl group content C C increases, the processability index I pro tends to increase accordingly. On the other hand, by making the carboxyl group content C C equal to or less than the above upper limit value, the processability is increased. Can be increased. On the other hand, by setting the carboxyl group content CC to the above lower limit value or more, the compression set of the resulting rubber cross-linked product can be further improved.
  • the absorbance area S A of the carboxylic anhydride group obtained by infrared spectroscopic analysis (carboxyl group which is an anhydride), compared nitrile group-containing copolymer rubber, definitive when subjected to infrared spectroscopic analysis
  • the area of absorbance corresponding to the carboxylic acid anhydride group, and the peak corresponding to the carboxylic acid anhydride group usually appears in the range of 1765 to 1795 cm ⁇ 1 , depending on the peak intensity.
  • the spectrum of the infrared spectroscopic analysis of the nitrile group-containing copolymer rubber according to Production Example 11 is shown in FIG.
  • infrared spectroscopic analysis is performed on a solid nitrile group-containing copolymer rubber by an ATR method (Attenuated Total Reflection) as an infrared spectrophotometer as a Fourier transform infrared spectrophotometer (FT-IR). ) And measuring the absorbance at each wavelength in accordance with “General Rules for Infrared Spectroscopy Methods” defined in JIS K0117: 2000.
  • a peak corresponding to the carboxylic acid anhydride group (a peak appearing in the range of 1770 to 1790 cm ⁇ 1 , and 1765 to 1795 cm ⁇ when the absorbance is relatively high). measuring the area of the appearing peak) in one of the ranges, which can be the absorbance area S a.
  • the absorbance area S A (the peak range of 1770 ⁇ 1790 cm -1, when the absorbance is relatively high, the peak range of 1765 ⁇ 1795 cm -1) peaks range corresponding to the carboxylic anhydride group absorbance at of the area, the absorbance area S a, absorbance (e.g., absorbance of the vertical axis in the spectrum shown in FIG. 1 (absorbance)) and wave number (e.g., the wave number of the horizontal axis in the spectrum shown in FIG. 1 (Wave number)) and Is the integrated value.
  • absorbance e.g., absorbance of the vertical axis in the spectrum shown in FIG. 1 (absorbance)
  • wave number e.g., the wave number of the horizontal axis in the spectrum shown in FIG. 1 (Wave number)
  • the absorbance area S A can be determined using what is provided as a standard measurement function of the Fourier transform infrared spectrophotometer as infrared spectrophotometer.
  • the absorbance area S A is preferably 0.09 cm ⁇ 1 or less, more preferably 0.07 cm ⁇ 1 or less, and even more preferably 0.06 cm ⁇ 1 or less. Absorbance area S A is too large, there workability index I pro also tends to increase along with this, whereas, by not more than the upper limit described above, it is possible to improve the workability.
  • the carboxyl group content C C , the absorbance area S A of the carboxylic anhydride group determined by infrared spectroscopic analysis, and the processability index I pro are not particularly limited.
  • a method for adjusting the content of an ethylenically unsaturated dicarboxylic acid monoester monomer unit in a nitrile group-containing copolymer rubber, ethylene forming an ethylenically unsaturated dicarboxylic acid monoester monomer unit A method for appropriately selecting the type of the unsaturated dicarboxylic acid monoester monomer, a method for controlling the thermal history of the nitrile group-containing copolymer rubber (for example, a method for controlling the drying method, drying temperature, drying time), The method of combining these methods suitably is mentioned.
  • the method of controlling the thermal history of the nitrile group-containing copolymer rubber, the ethylenically unsaturated dicarboxylic acid monoester single amount The production of acid anhydrides derived from body units can be effectively suppressed, thereby making it possible to appropriately lower the workability index I pro .
  • the polymer Mooney viscosity (ML1 + 4, 100 ° C.) of the nitrile group-containing copolymer rubber of the present invention is preferably 10 to 200, more preferably 15 to 100, still more preferably 20 to 80, and particularly preferably 30 to 60. .
  • the polymer Mooney viscosity is preferably 10 to 200, more preferably 15 to 100, still more preferably 20 to 80, and particularly preferably 30 to 60.
  • the method for producing the nitrile group-containing copolymer rubber of the present invention is not particularly limited, but is produced by copolymerizing the above-described monomers and hydrogenating the carbon-carbon double bonds in the resulting copolymer. can do.
  • the polymerization method is not particularly limited and may be a known emulsion polymerization method or solution polymerization method. From the viewpoint of industrial productivity, the emulsion polymerization method is preferable. In emulsion polymerization, in addition to an emulsifier, a polymerization initiator, and a molecular weight modifier, a commonly used polymerization auxiliary material can be used.
  • nonionic emulsifiers such as polyoxyethylene alkyl ether, polyoxyethylene alkyl phenol ether, polyoxyethylene alkyl ester, polyoxyethylene sorbitan alkyl ester; myristic acid, palmitic acid, oleic acid
  • anionic emulsifiers such as salts of fatty acids such as linolenic acid, alkylbenzene sulfonates such as sodium dodecylbenzene sulfonate, polycondensates of naphthalene sulfonate and formalin, higher alcohol sulfates, alkyl sulfosuccinates; , ⁇ -unsaturated carboxylic acid sulfoesters, ⁇ , ⁇ -unsaturated carboxylic acid sulfate esters, sulfoalkyl aryl ethers and other copolymerizable emuls
  • the polymerization initiator is not particularly limited as long as it is a radical initiator, but inorganic peroxides such as potassium persulfate, sodium persulfate, ammonium persulfate, potassium perphosphate, hydrogen peroxide; t-butyl peroxide, cumene Hydroperoxide, p-menthane hydroperoxide, di-t-butyl peroxide, t-butylcumyl peroxide, acetyl peroxide, isobutyryl peroxide, octanoyl peroxide, dibenzoyl peroxide, 3, 5, 5 Organic peroxides such as trimethylhexanoyl peroxide and t-butylperoxyisobutyrate; azobisisobutyronitrile, azobis-2,4-dimethylvaleronitrile, azobiscyclohexanecarbonitrile, methyl azobisisobutyrate, etc.
  • inorganic peroxides
  • polymerization initiators can be used alone or in combination of two or more.
  • an inorganic or organic peroxide is preferable.
  • a peroxide as the polymerization initiator, use it as a redox polymerization initiator in combination with a reducing agent such as sodium bisulfite, ferrous sulfate, sodium formaldehyde sulfoxylate and sodium ethylenediaminetetraacetate. You can also.
  • chelating agents such as sodium ethylenediaminetetraacetate tetrahydrate and builders such as sodium carbonate and sodium sulfate can be used in combination.
  • the addition amount of the polymerization initiator is preferably 0.01 to 2 parts by weight with respect to 100 parts by weight of the monomer used for the polymerization.
  • the molecular weight modifier is not particularly limited, but mercaptans such as t-dodecyl mercaptan, n-dodecyl mercaptan, octyl mercaptan; halogenated hydrocarbons such as carbon tetrachloride, methylene chloride, methylene bromide; ⁇ -methylstyrene dimer And sulfur-containing compounds such as tetraethylthiuram disulfide, dipentamethylene thiuram disulfide, and diisopropylxanthogen disulfide. These can be used alone or in combination of two or more.
  • the amount of the molecular weight modifier used is preferably 0.1 to 0.8 parts by weight with respect to 100 parts by weight of the total monomers.
  • Water is usually used as the emulsion polymerization medium.
  • the amount of water is preferably 80 to 500 parts by weight, more preferably 80 to 300 parts by weight with respect to 100 parts by weight of the monomer used for the polymerization.
  • polymerization auxiliary materials such as a stabilizer, a dispersant, a pH adjuster, an oxygen scavenger, and a particle size adjuster can be used as necessary. In using these, neither the kind nor the usage-amount is specifically limited.
  • the obtained copolymer may be subjected to hydrogenation (hydrogenation reaction) as necessary.
  • Hydrogenation may be carried out by a known method. After coagulating a latex of a copolymer obtained by emulsion polymerization, an oil layer hydrogenation method in which hydrogenation is performed in an oil layer, or a latex of the obtained copolymer is hydrogenated as it is. And water layer hydrogenation method.
  • the copolymer latex prepared by emulsion polymerization is preferably dissolved in an organic solvent through salting out, coagulation with alcohol, filtration and drying.
  • a hydrogenation reaction oil layer hydrogenation method
  • the resulting hydride is poured into a large amount of water, solidified, washed with water, filtered and dried to obtain the nitrile group-containing copolymer rubber of the present invention. Can do. In some cases, centrifugal dehydration may be performed.
  • a known coagulant such as sodium chloride, calcium chloride, aluminum sulfate, magnesium sulfate can be used. Moreover, it may replace with solidification by salting out and may perform coagulation using alcohol, such as methanol and isopropyl alcohol.
  • the solvent for the oil layer hydrogenation method is not particularly limited as long as it is a liquid organic compound that dissolves the copolymer obtained by emulsion polymerization, but benzene, chlorobenzene, toluene, xylene, hexane, cyclohexane, tetrahydrofuran, methyl ethyl ketone, ethyl acetate. Cyclohexanone and acetone are preferably used.
  • any known selective hydrogenation catalyst can be used without limitation.
  • Palladium-based catalysts and rhodium-based catalysts are preferable, and palladium-based catalysts (such as palladium acetate, palladium chloride and palladium hydroxide) are preferred. More preferred. Two or more of these may be used in combination. In this case, it is preferable to use a palladium-based catalyst as the main active ingredient.
  • These catalysts are usually used by being supported on a carrier.
  • the carrier include silica, silica-alumina, alumina, diatomaceous earth, activated carbon and the like.
  • the amount of catalyst used is preferably 10 to 20000 ppm by weight, more preferably 50 to 15000 ppm by weight, based on the copolymer.
  • the latex of the copolymer prepared by the emulsion polymerization is diluted with water as necessary to perform a hydrogenation reaction.
  • the water layer hydrogenation method is a water layer direct hydrogenation method in which hydrogen is supplied to a reaction system in the presence of a hydrogenation catalyst to perform hydrogenation, and reduction and hydrogenation are performed in the presence of an oxidizing agent, a reducing agent and an activator.
  • An aqueous layer indirect hydrogenation method can be mentioned, and among these, the aqueous layer direct hydrogenation method is preferable.
  • the concentration of the copolymer in the aqueous layer is preferably 40% by weight or less in order to prevent aggregation.
  • a hydrogenation catalyst will not be specifically limited if it is a compound which is hard to decompose
  • the palladium catalyst include palladium salts of carboxylic acids such as formic acid, propionic acid, lauric acid, succinic acid, oleic acid, and phthalic acid; palladium chloride, dichloro (cyclooctadiene) palladium, dichloro (norbornadiene) palladium, Palladium chloride such as ammonium hexachloropalladium (IV); Iodide such as palladium iodide; Palladium nitrate; Palladium sulfate dihydrate and the like.
  • palladium salts of carboxylic acids, palladium chloride, and palladium nitrate are particularly preferable.
  • the amount of the hydrogenation catalyst used may be appropriately determined, but is preferably 5 to 20000 ppm by weight, more preferably 10 to 15000 ppm by weight, based on the copolymer obtained by polymerization.
  • the hydrogenation catalyst in the latex is removed after completion of the hydrogenation reaction.
  • an adsorbent such as activated carbon or ion exchange resin is added to adsorb the hydrogenation catalyst with stirring, or a complex of the hydrogenation catalyst is formed using a complexing agent together with an oxidizing agent or a reducing agent.
  • the latex after the hydrogenation reaction obtained in this manner is subjected to coagulation by alcohol or salting out such as methanol or isopropyl alcohol, water washing, and filtration, and thus obtained.
  • alcohol or salting out such as methanol or isopropyl alcohol
  • water washing, and filtration By drying the hydrated crumb, the nitrile group-containing copolymer rubber of the present invention can be obtained.
  • a known coagulant such as sodium chloride, calcium chloride, aluminum sulfate, magnesium sulfate can be used. In some cases, centrifugal dehydration may be performed.
  • the temperature during drying is preferably 40 to 100 ° C. More preferably, the drying time is 60 to 90 ° C., and the drying time is preferably 0.5 to 12 hours, more preferably 1 to 6 hours.
  • the drying temperature is preferably 100 to 200 ° C., more preferably 120 to 170 ° C., and the drying time is preferably 1 to 20 minutes, more preferably 2 to 15 minutes. .
  • the drying time is preferably 1 to 20 minutes, more preferably 2 to 15 minutes.
  • an anti-aging agent can be added to the oil layer or water layer before solidification.
  • the anti-aging agent is not particularly limited, but 2,6-di-t-butyl-4-cresol (Antage BHT, manufactured by Kawaguchi Chemical Co., Ltd.), 2,2′-methylenebis (4-methyl-6-tert- Butylphenol) (Sandant® 2246, manufactured by Sanshin Chemical Industry Co., Ltd.), bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide (Sandant® 103, manufactured by Sanshin Chemical Industry Co., Ltd.), pentaerythritol tetrakis [ 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (Irganox 1010, manufactured by BASF Japan), octadecyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate (Irganox 1076, manufactured
  • crosslinkable rubber composition of the present invention comprises the nitrile group-containing copolymer rubber of the present invention and a crosslinking agent.
  • the crosslinking agent is not particularly limited as long as it can crosslink the nitrile group-containing copolymer rubber of the present invention, and examples thereof include a sulfur crosslinking agent, an organic peroxide crosslinking agent, and a polyamine-based crosslinking agent. Among these, polyamine-based crosslinking agents are preferable.
  • Sulfur-based cross-linking agents include powdered sulfur, sulfur white, precipitated sulfur, colloidal sulfur, surface-treated sulfur, insoluble sulfur, etc .; sulfur chloride, sulfur dichloride, morpholine disulfide, alkylphenol disulfide, dibenzothiazyl disulfide, caprolactam disulfide (N, N′-dithio-bis (hexahydro-2H-azepinone-2)), phosphorus-containing polysulfides, sulfur-containing compounds such as polymer polysulfides; tetramethylthiuram disulfide, selenium dimethyldithiocarbamate, 2- (4 ′ -Morpholinodithio) sulfur donating compounds such as benzothiazole; and the like. These can be used individually by 1 type or in combination of multiple types.
  • organic peroxide crosslinking agents include dicumyl peroxide, cumene hydroperoxide, t-butylcumyl peroxide, paramentane hydroperoxide, di-t-butyl peroxide, 1,3-bis (t-butylperoxyisopropyl) benzene, 1,4-bis (t-butylperoxyisopropyl) benzene, 1,1-di-t-butylperoxy-3,3-trimethylcyclohexane, 4,4-bis- (t-butyl-peroxy) -n-butylvale 2,5-dimethyl-2,5-di-t-butylperoxyhexane, 2,5-dimethyl-2,5-di-t-butylperoxyhexyne-3, 1,1-di-t-butyl Peroxy-3,5,5-trimethylcyclohexane, p-chlorobenzoyl peroxide, t-butyl
  • the polyamine-based crosslinking agent is not particularly limited as long as it is a compound having two or more amino groups or a compound having two or more amino groups at the time of crosslinking.
  • a compound in which a plurality of hydrogen atoms of a group hydrocarbon are substituted with an amino group or a hydrazide structure (a structure represented by —CONHNH 2 , CO represents a carbonyl group), and a compound that is in the form of the compound upon crosslinking are preferred .
  • polyamine-based cross-linking agent examples include aliphatic polyvalent compounds such as hexamethylene diamine, hexamethylene diamine carbamate, N, N-dicinnamylidene-1,6-hexane diamine, tetramethylene pentamine, and hexamethylene diamine cinnamaldehyde adduct.
  • aliphatic polyvalent amines and aromatic polyvalent amines are preferable from the viewpoint that the effects of the present invention can be made more remarkable, and hexamethylenediamine carbamate and 2,2-bis [ 4- (4-Aminophenoxy) phenyl] propane is more preferred, and hexamethylenediamine carbamate is particularly preferred.
  • the content of the crosslinking agent in the crosslinkable rubber composition of the present invention is not particularly limited, but is preferably 0.1 to 20 parts by weight, more preferably 1 to 1 part by weight based on 100 parts by weight of the nitrile group-containing copolymer rubber. 15 parts by weight.
  • crosslinking agent when a polyamine crosslinking agent is used as the crosslinking agent, it is preferable to further contain a basic crosslinking accelerator.
  • basic crosslinking accelerators include compounds represented by the following general formula (1), basic crosslinking accelerators having a cyclic amidine structure, guanidine basic crosslinking accelerators, and aldehyde amine basic crosslinking accelerators. Agents and the like.
  • R 1 and R 2 may each independently have an alkyl group having 1 to 12 carbon atoms which may have a substituent, or may have a substituent.
  • It is a cycloalkyl group having 5 to 12 carbon atoms.
  • R 1 and R 2 are each an optionally substituted alkyl group having 1 to 12 carbon atoms or an optionally substituted cycloalkyl group having 5 to 12 carbon atoms.
  • a cycloalkyl group having 5 to 12 carbon atoms which may have a group is preferable, and a cycloalkyl group having 5 to 8 carbon atoms which may have a substituent is particularly preferable.
  • R 1 and R 2 are preferably not substituted.
  • R 1 and R 2 have a substituent include a hydroxyl group, an alkoxy group, an alkoxycarbonyl group, an amino group, and a halogen atom.
  • a compound represented by the following general formula (2) is more preferable from the viewpoint that processability and scorch stability can be further improved.
  • R 3 and R 4 are each independently a cycloalkyl group having 5 to 8 carbon atoms which may have a substituent.
  • R 3 and R 4 are cycloalkyl groups having 5 to 8 carbon atoms which may have a substituent, but may be cycloalkyl groups which may have a substituent having 5 or 6 carbon atoms. Is preferable, and a cycloalkyl group which may have a substituent having 6 carbon atoms is more preferable. R 3 and R 4 preferably have no substituent.
  • R 3 and R 4 have a substituent include a hydroxyl group, an alkoxy group, an alkoxycarbonyl group, an amino group, and a halogen atom.
  • Specific examples of the compound represented by the general formula (1) include dicycloalkylamines such as dicyclopentylamine, dicyclohexylamine and dicycloheptylamine; N-methylcyclopentylamine, N-butylcyclopentylamine and N-heptyl.
  • Examples of the basic crosslinking accelerator having a cyclic amidine structure include 1,8-diazabicyclo [5,4,0] undecene-7 (hereinafter sometimes abbreviated as “DBU”) and 1,5-diazabicyclo [4, 3,0] nonene-5 (hereinafter sometimes abbreviated as “DBN”), 1-methylimidazole, 1-ethylimidazole, 1-phenylimidazole, 1-benzylimidazole, 1,2-dimethylimidazole, 1-ethyl- 2-methylimidazole, 1-methoxyethylimidazole, 1-phenyl-2-methylimidazole, 1-benzyl-2-methylimidazole, 1-methyl-2-phenylimidazole, 1-methyl-2-benzylimidazole, 1,4 -Dimethylimidazole, 1,5-dimethylimidazole, 1,2,4-trimethylimidazole, 1,4- Methyl-2-ethylimidazole,
  • 1,8-diazabicyclo [5,4,0] undecene-7 and 1,5-diazabicyclo [4,3,0] nonene-5 are preferred, , 8-diazabicyclo [5,4,0] undecene-7 is more preferred.
  • the guanidine-based basic crosslinking accelerator include tetramethylguanidine, tetraethylguanidine, diphenylguanidine, 1,3-di-ortho-tolylguanidine, orthotolyl biguanide and the like.
  • aldehyde amine basic crosslinking accelerator include n-butyraldehyde aniline and acetaldehyde ammonia.
  • guanidine basic crosslinking accelerators compounds represented by the above general formula (1), guanidine basic crosslinking accelerators, and basic crosslinking accelerators having a cyclic amidine structure are preferable.
  • a compound represented by the formula and a basic crosslinking accelerator having a cyclic amidine structure are more preferred.
  • the compound represented by the general formula (1) may be a mixture of an alkylene glycol or an alcohol such as an alkyl alcohol having 5 to 20 carbon atoms, and an inorganic acid and / or an organic acid. May be included. Further, as the compound represented by the general formula (1), a salt is formed by the compound represented by the general formula (1) and the inorganic acid and / or organic acid, and a complex is formed with alkylene glycol. It may be.
  • the basic crosslinking accelerator having a cyclic amidine structure may form a salt with an organic carboxylic acid or an alkyl phosphoric acid.
  • the blending amount in the crosslinkable rubber composition of the present invention is preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the nitrile group-containing copolymer rubber. More preferably, it is 0.2 to 15 parts by weight, still more preferably 0.5 to 10 parts by weight.
  • the cross-linkable rubber composition of the present invention includes compounding agents commonly used in the rubber field, for example, reinforcing agents such as carbon black and silica, fillers such as calcium carbonate, talc and clay, oxidation Metal oxides such as zinc and magnesium oxide, ⁇ , ⁇ -ethylenically unsaturated carboxylic acid metal salts such as zinc methacrylate and zinc acrylate, co-crosslinking agents, crosslinking aids, crosslinking retarders, anti-aging agents, antioxidants Agents, light stabilizers, scorch inhibitors such as primary amines, activators such as diethylene glycol, coupling agents, plasticizers, processing aids, lubricants, adhesives, lubricants, flame retardants, antifungal agents, acid acceptors, An antistatic agent, a pigment, a foaming agent, etc. can be mix
  • the compounding amount of these compounding agents is not particularly limited as long as it does not impair the object and effect of the present invention, and an oxidation
  • the coupling agent examples include silane coupling agents, aluminum coupling agents, titanate coupling agents, and the like.
  • the silane coupling agent is not particularly limited, and specific examples thereof include ⁇ -mercaptopropyltrimethoxysilane, ⁇ -mercaptomethyltrimethoxylane, ⁇ -mercaptomethyltriethoxylane, ⁇ -mercaptohexamethyldisilazane, bis Silane coupling agents containing sulfur such as (3-triethoxysilylpropyl) tetrasulfane and bis (3-triethoxysilylpropyldisulfane); ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropyl Epoxy group-containing silane coupling agents such as methyldimethoxysilane, ⁇ - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, ⁇ -mercaptopropyltrimethoxysilane,
  • the aluminum coupling agent is not particularly limited, and specific examples thereof include acetoalkoxyaluminum diisopropylate.
  • the titanate coupling agent is not particularly limited, and specific examples thereof include isopropyl triisostearoyl titanate, isopropyl tris (dioctylpyrophosphate) titanate, isopropyl tri (N-aminoethyl-aminoethyl) titanate, tetraoctyl bis ( Ditridecyl phosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, bis (dioctylpyrophosphate) oxyacetate titanate, bis (dioctylpyrophosphate) ethylene titanate, tetraisopropyl Bis (dioctyl phosphite
  • carbon black examples include furnace black, acetylene black, thermal black, channel black, Austin black, and graphite. These can be used alone or in combination.
  • silica examples include natural silica such as quartz powder and silica powder; synthetic silica such as anhydrous silicic acid (silica gel, aerosil, etc.) and hydrous silicic acid. Among these, synthetic silica is preferable.
  • These silicas may be surface-treated with a coupling agent or the like. As the coupling agent used for the surface treatment, for example, those described above can be used.
  • the co-crosslinking agent is not particularly limited, but is preferably a low molecular or high molecular compound having a plurality of radical-reactive unsaturated groups in the molecule.
  • a polyfunctional vinyl compound such as divinylbenzene or divinylnaphthalene; Isocyanurates such as allyl isocyanurate and trimethallyl isocyanurate; cyanurates such as triallyl cyanurate; maleimides such as N, N′-m-phenylene dimaleimide; diallyl phthalate, diallyl isophthalate, diallyl maleate, diallyl Allyl esters of polyvalent acids such as fumarate, diallyl sebacate, triallyl phosphate; diethylene glycol bisallyl carbonate; ethylene glycol diallyl ether, triallyl ether of trimethylolpropane, pentaerythritol Allyl ethers such as partial trityl ethers of trit; ally
  • the plasticizer is not particularly limited, but trimellitic acid plasticizer, pyromellitic acid plasticizer, ether ester plasticizer, polyester plasticizer, phthalic acid plasticizer, adipate ester plasticizer, phosphoric acid
  • trimellitic acid plasticizer pyromellitic acid plasticizer
  • ether ester plasticizer polyester plasticizer
  • phthalic acid plasticizer adipate ester plasticizer
  • phosphoric acid An ester plasticizer, a sebacic acid ester plasticizer, an alkyl sulfonic acid ester compound plasticizer, an epoxidized vegetable oil plasticizer, or the like can be used.
  • trimellitic acid tri-2-ethylhexyl trimellitic acid isononyl ester, trimellitic acid mixed linear alkyl ester, dipentaerythritol ester, pyromellitic acid 2-ethylhexyl ester, polyether ester (molecular weight 300 to About 5,000), bis [2- (2-butoxyethoxy) ethyl adipate], dioctyl adipate, polyester based on adipic acid (molecular weight about 300 to 5000), dioctyl phthalate, diisononyl phthalate, dibutyl phthalate, phosphoric acid
  • examples include tricresyl, dibutyl sebacate, alkylsulfonic acid phenyl ester, epoxidized soybean oil, diheptanoate, di-2-ethylhexanoate, and didecanoate. These can be used alone or in combination.
  • examples of such rubbers include acrylic rubber, ethylene-acrylic acid copolymer rubber, styrene-butadiene copolymer rubber, polybutadiene rubber, ethylene-propylene copolymer rubber, ethylene-propylene-diene terpolymer rubber, Examples include epichlorohydrin rubber, fluorine rubber, urethane rubber, chloroprene rubber, silicone rubber, natural rubber, and polyisoprene rubber.
  • the blending amount in the crosslinkable rubber composition is preferably 30 with respect to 100 parts by weight of the nitrile group-containing copolymer rubber of the present invention. It is not more than parts by weight, more preferably not more than 20 parts by weight, still more preferably not more than 10 parts by weight.
  • the crosslinkable rubber composition of the present invention is prepared by mixing each of the above components preferably in a non-aqueous system.
  • the method for preparing the crosslinkable rubber composition of the present invention is not limited, but usually the components excluding the crosslinker and heat-labile components are primarily kneaded with a mixer such as a Banbury mixer, an intermixer, or a kneader. Then, it can transfer to an open roll etc., and can prepare by adding a crosslinking agent and a heat unstable component, and carrying out secondary kneading
  • the primary kneading is usually performed at a temperature of 10 to 200 ° C., preferably 30 to 180 ° C.
  • the reaction is performed at a temperature of 20 to 60 ° C. for 1 minute to 1 hour, preferably 1 minute to 30 minutes.
  • Cross-linked rubber The cross-linked rubber of the present invention is obtained by cross-linking the cross-linkable rubber composition of the present invention described above.
  • the rubber cross-linked product of the present invention is formed by using the cross-linkable rubber composition of the present invention, and is molded by a molding machine corresponding to a desired shape, for example, an extruder, an injection molding machine, a compressor, a roll, etc., and heated. Can be produced by carrying out a crosslinking reaction and fixing the shape as a crosslinked product.
  • crosslinking may be performed after molding in advance, or crosslinking may be performed simultaneously with molding.
  • the molding temperature is usually 10 to 200 ° C, preferably 25 to 120 ° C.
  • the crosslinking temperature is usually 100 to 200 ° C., preferably 130 to 190 ° C.
  • the crosslinking time is usually 1 minute to 24 hours, preferably 2 minutes to 1 hour.
  • secondary cross-linking may be performed by heating.
  • a heating method a general method used for crosslinking of rubber such as press heating, steam heating, oven heating, and hot air heating may be appropriately selected.
  • the rubber cross-linked product of the present invention thus obtained is obtained using the above-described nitrile group-containing copolymer rubber of the present invention, and is excellent in compression set resistance. For this reason, the rubber cross-linked product of the present invention makes use of such characteristics, such as O-rings, packings, diaphragms, oil seals, shaft seals, bearing seals, well head seals, shock absorber seals, long life coolant (LLC), etc.
  • LLC long life coolant
  • Coolant seal oil coolant seal, seal for pneumatic equipment, seals for CFCs, fluorohydrocarbons or carbon dioxide used for air conditioner cooling devices and air conditioner refrigerator compressors , Supercritical carbon dioxide or subcritical carbon dioxide sealing seals used for precision cleaning media, rolling devices (rolling bearings, automotive hub units, automotive water pumps, linear guide devices, ball screws, etc.) Seals, valves and valve seals , BOP (Blow Out Preventer), various sealing materials such as bladders; Intake manifold gaskets attached to the connecting portion between the intake manifold and the cylinder head, Cylinder head gaskets attached to the connecting portion between the cylinder block and the cylinder head, rockers A pair of rocker cover gaskets attached to the connecting part between the cover and the cylinder head, an oil pan gasket attached to the connecting part between the oil pan and the cylinder block or the transmission case, and a unit cell including a positive electrode, an electrolyte plate and a negative electrode.
  • Carboxyl group content C C After adding 100 mL of pyridine to 0.2 g of 2 mm square nitrile group-containing copolymer rubber and stirring for 16 hours, using a 0.02N alcoholic potassium hydroxide solution of potassium hydroxide at room temperature while stirring, By titration with rain as an indicator, the carboxyl group content CC was determined as the number of moles of carboxyl groups relative to 100 g of rubber (unit: ephr).
  • Absorbance area S A of a carboxylic acid anhydride group by infrared spectroscopy Absorbance area S A of a carboxylic acid anhydride group, to a nitrile group-containing copolymer rubber of a solid, the ATR method (Attenuated Total Reflection), as an infrared spectrophotometer, a Fourier transform infrared spectrophotometer (FT Infrared spectroscopic analysis is performed in accordance with “General Rules of Infrared Spectroscopy Methods” defined in JIS K0117: 2000. From the results of infrared spectroscopic analysis, a range of 1770 to 1790 cm ⁇ 1 is used. The area of the absorbance peak appearing in Fig.
  • the measurement in order to suppress the measurement error of the absorbance area as much as possible, the measurement was performed at room temperature while pressing the entire surface of the prism so as to cover it with rubber without any gap.
  • the nitrile group-containing copolymer rubber as a measurement sample was measured in a state where it was not diluted with another material (that is, a state where the concentration was 100% by weight). Further, the absorbance area S A was determined using what is provided as a standard measurement function of the Fourier transform infrared spectrophotometer "FTS7000".
  • the iodine value of the nitrile group-containing copolymer rubber was measured according to JIS K 6235.
  • composition of nitrile group-containing copolymer rubber The content ratio of each monomer unit constituting the nitrile group-containing copolymer rubber was measured by the following method. That is, the content ratio of mono-n-butyl maleate unit, mono-n-butyl fumarate unit, monocyclohexyl fumarate unit and mono-n-butyl itaconate unit was determined by hydrogenation according to the above-mentioned “carboxyl group content” measurement method.
  • the number of moles of carboxyl groups relative to 100 g of the nitrile group-containing copolymer rubber was determined, and the determined number of moles were determined as mono n-butyl maleate unit, mono n-butyl fumarate unit, monocyclohexyl unit fumarate and mono n itaconate.
  • -Calculated by converting to the amount of butyl alone.
  • the content ratio of 1,3-butadiene units (including hydrogenated portions) was calculated by measuring the iodine value (according to JIS K6235) using a nitrile group-containing copolymer rubber before hydrogenation.
  • the content ratio of the acrylonitrile unit was calculated according to JIS K6384 by measuring the nitrogen content in the nitrile group-containing copolymer rubber after hydrogenation by the semi-micro Kjeldahl method or the modified Dumas method.
  • the content ratio of the n-butyl acrylate unit and the methoxyethyl acrylate unit was calculated as the balance of each monomer unit.
  • the Mooney viscosity (polymer Mooney viscosity) (ML1 + 4, 100 ° C.) of the nitrile group-containing copolymer rubber was measured according to JIS K6300.
  • the compound-state crosslinkable rubber composition was visually observed, and in accordance with the following criteria, evaluation was made on the sheet-like compound fabric state and cracks and poor fusion at the time of preparing a sample for a compression set test described later.
  • A There were no cracks or poor fusion.
  • C Cracking / fusion failure occurred at a rate of 1 or more per 5
  • the compression set test crosslinkable rubber composition was subjected to primary crosslinking by pressing at a temperature of 170 ° C. for 25 minutes using a mold to obtain a cylindrical rubber crosslinked product having a diameter of 29 mm and a height of 12.5 mm.
  • the obtained rubber cross-linked product was transferred to a gear-type oven and subjected to secondary cross-linking at 170 ° C. for 4 hours to produce a cylindrical rubber cross-linked product.
  • the obtained rubber cross-linked product was placed in a 150 ° C. environment for 168 hours in a state where the rubber cross-linked product was compressed 25% in accordance with JIS K6262, and then the compression set was measured. The smaller this value, the better the compression set resistance.
  • Production Example 1 (Production of nitrile group-containing copolymer rubber (n1))
  • a reactor 180 parts of ion-exchanged water, 25 parts of a 10% sodium dodecylbenzenesulfonate aqueous solution, 5 parts of a 10% sodium naphthalene sulfonate formalin condensate, 15 parts of acrylonitrile, 39 parts of n-butyl acrylate
  • 5.5 parts of mono-n-butyl maleate and 0.75 part of t-dodecyl mercaptan (molecular weight modifier) were charged in this order, and the internal gas was replaced with nitrogen three times.
  • t-dodecyl mercaptan molecular weight modifier
  • the reactor was kept at 10 ° C., and 0.1 parts of cumene hydroperoxide (polymerization initiator), a reducing agent, a chelating agent, and an appropriate amount of builder were charged, and the polymerization reaction was continued while stirring, with a polymerization conversion of 80 %, 2,4,6,6-tetramethylpiperidine-1-oxyl aqueous solution (polymerization terminator) having a concentration of 2.5 wt% was added to stop the polymerization reaction. Subsequently, the residual monomer was removed at a water temperature of 60 ° C. to obtain a latex of nitrile group-containing copolymer rubber (X1) (solid content concentration 25% by weight).
  • X1 solid content concentration 25% by weight
  • Sodium chloride equivalent to twice the molar equivalent of Pd metal in palladium chloride was added to palladium chloride to obtain an aqueous palladium solution. Then, to the obtained aqueous palladium solution, polyvinylpyrrolidone having a weight average molecular weight of 5,000 is added in an amount which is 5 times by weight with respect to Pd metal in palladium chloride, and further an aqueous potassium hydroxide solution is added. Thus, an aqueous catalyst solution having a pH of 12.0 was prepared.
  • a nitrile group-containing copolymer rubber (in order that the palladium content relative to the dry weight of the rubber contained in the latex of the nitrile rubber (X1) obtained above is 2,500 ppm by weight. X1) latex and aqueous catalyst solution were added, and hydrogenation reaction was performed at a hydrogen pressure of 3 MPa, a temperature of 50 ° C., and a solid content concentration of 20% by weight for 6 hours, and the hydrogenated nitrile group-containing copolymer rubber (n1) Latex was obtained.
  • the pH of the latex obtained above was adjusted to 7.0, and 2 of dimethylglyoxime and dimethylglyoxime corresponding to 5 times the amount of Pd metal contained in palladium chloride used in the hydrogenation reaction.
  • a mixed aqueous solution of potassium hydroxide corresponding to a double molar amount was added, and a hydrogen peroxide solution corresponding to a 30 times molar amount of Pd metal was further added.
  • the mixture was heated to 80 ° C. and stirred for 5 hours, an insoluble complex was precipitated in the latex, which was removed by filtration.
  • the resulting nitrile group-containing copolymer rubber (n1) latex was adjusted to pH 4 with 1 wt% sulfuric acid, 100 parts of sodium chloride was added to 100 parts of the copolymer, and the pH was adjusted to 3 with sulfuric acid. It was added to a volume of ion-exchanged water with stirring and solidified.
  • the water-containing crumb of the obtained nitrile group-containing copolymer rubber (n1) was washed twice with 1 L of ion-exchanged water, centrifuged and dehydrated, and then dried with hot air at 80 ° C. for 4 hours to obtain a solid nitrile A group-containing copolymer rubber (n1) was obtained.
  • Nitrile group-containing copolymer rubber (n2), (n4), (n5), (n6), (n9), iodine value of (n13), polymer Mooney viscosity (ML1 + 4, 100 ° C.), single amount
  • Production Examples 3, 7, 8 (Production of nitrile group-containing copolymer rubber (n3), (n7), (n8))
  • the type and amount of the monomer used for the polymerization are changed as shown in Table 1, and the polymerization conversion rate of the polymerization reaction and the amount of palladium catalyst in the hydrogenation reaction are changed as shown in Table 1, and
  • Table 1 When drying the water-containing crumb, except that the obtained water-containing crumb was dried by kneading with a Brabender at 150 ° C. for 5 minutes, in the same manner as in Production Example 1, Solid nitrile group-containing copolymer rubbers (n3), (n7), and (n8) were obtained.
  • Production Example 11 (Production of nitrile group-containing copolymer rubber (n11)) A solid nitrile group-containing copolymer rubber (n11) was obtained in the same manner as in Production Example 8, except that the drying conditions by kneading using a Brabender were changed to 150 ° C. and 20 minutes.
  • the iodine value of the obtained nitrile group-containing copolymer rubber (n11), polymer Mooney viscosity (ML1 + 4, 100 ° C.), monomer composition, carboxyl group content C C , absorbance area of carboxylic acid anhydride group S A and processability index I pro (I pro C C ⁇ S A ) were as shown in Table 1.
  • Example 1 Using a Banbury mixer, 100 parts of the nitrile group-containing copolymer rubber (n1) obtained in Production Example 1, 40 parts of FEF carbon (trade name “Seast SO”, carbon black manufactured by Tokai Carbon Co., Ltd.) Mellitic acid tri-2-ethylhexyl (trade name “Adekasizer C-8”, plasticizer, manufactured by ADEKA), 1 part stearic acid, polyoxyethylene alkyl ether phosphate ester (trade name “phosphanol RL210”) 1 part of Toho Chemical Industries, Ltd., processing aid), and 4,4′-di- ( ⁇ , ⁇ ′-dimethylbenzyl) diphenylamine (trade name “NOCRACK CD”, manufactured by Ouchi Shinsei Chemical Co., Ltd., anti-aging agent ) 1.5 parts is added and kneaded, then the mixture is transferred to a roll and 1,8-diazabicyclo [5,4,0] undecene-7 (DBU) (trade name: “R
  • Examples 2 to 10 In place of the nitrile group-containing copolymer rubber (n1) obtained in Production Example 1, the nitrile group-containing copolymer rubbers (n2) to (n10) obtained in Production Examples 2 to 10 were used and crosslinked.
  • a crosslinkable rubber composition was obtained in the same manner as in Example 1 except that the amount of hexamethylenediamine carbamate as an agent was changed to the amount shown in Table 2, and evaluated in the same manner. The results are shown in Table 2.
  • ND in “Absorbance area S A of carboxylic acid anhydride group” is a peak in the range of 1770 to 1790 cm ⁇ 1 , and a peak derived from the carboxylic acid anhydride group is visually or automatically peaked. It means that it was not detected by the detection function.
  • the workability index I pro C C ⁇ S A
  • the amount of hexamethylenediamine carbamate blended is shown as an amount relative to 100 parts of the nitrile group-containing copolymer rubber.
  • the Mooney viscosity change ⁇ ML is small, the compound fabric is in good condition, cracks and poor fusion in the compound are adequately suppressed, and it has excellent moldability, and also contains such nitrile groups
  • the crosslinked rubber obtained using the copolymer rubber had a low compression set rate and was excellent in compression set resistance (Examples 1 to 10).

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PCT/JP2018/006684 2017-03-17 2018-02-23 ニトリル基含有共重合体ゴム WO2018168396A1 (ja)

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EP18766827.2A EP3597677B1 (en) 2017-03-17 2018-02-23 Method for producing a nitrile group-containing copolymer rubber
CA3056037A CA3056037A1 (en) 2017-03-17 2018-02-23 Nitrile group-containing copolymer rubber
JP2019505822A JP7088164B2 (ja) 2017-03-17 2018-02-23 ニトリル基含有共重合体ゴム
CN201880018369.1A CN110461892B (zh) 2017-03-17 2018-02-23 含腈基共聚物橡胶
RU2019128492A RU2752164C2 (ru) 2017-03-17 2018-02-23 Сополимерный каучук, содержащий нитрильные группы
US16/493,270 US20200131293A1 (en) 2017-03-17 2018-02-23 Nitrile group-containing copolymer rubber
KR1020197027179A KR102475647B1 (ko) 2017-03-17 2018-02-23 니트릴기 함유 공중합체 고무
BR112019019066A BR112019019066A2 (pt) 2017-03-17 2018-02-23 borracha de copolímero contendo grupo nitrila, composição de borracha reticulável, e, borracha reticulada.
MX2019010745A MX2019010745A (es) 2017-03-17 2018-02-23 Caucho de copolimero que contiene grupo nitrilo.
US17/592,755 US11639408B2 (en) 2017-03-17 2022-02-04 Nitrile group-containing copolymer rubber

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JP2010144176A (ja) * 2008-12-19 2010-07-01 Lanxess Deutschland Gmbh 加硫可能なポリマー組成物
JP2016006132A (ja) * 2014-06-20 2016-01-14 日本ゼオン株式会社 架橋性ゴム組成物、ゴム架橋物および複合体

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